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US3523075A - Control of purge velocity and volume in molecular sieve separation of hydrocarbons - Google Patents

Control of purge velocity and volume in molecular sieve separation of hydrocarbons Download PDF

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US3523075A
US3523075A US712166A US3523075DA US3523075A US 3523075 A US3523075 A US 3523075A US 712166 A US712166 A US 712166A US 3523075D A US3523075D A US 3523075DA US 3523075 A US3523075 A US 3523075A
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purge
straight chain
adsorption
medium
desorption
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Richard W Stokeld Jr
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Texaco Inc
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Texaco Inc
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
    • C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves

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  • the present invention relates to an improved method of separating straight chain hydrocarbons from a mixture thereof with non-straight chain hydrocarbons. More particularly, the present invention is directed to an improved vapor phase method of separating relatively long straight chain hydrocarbons from hydrocarbon mixtures at elevated temperatures and superatmospheric pressures using a molecular sieve selective adsorbent of Type A structure.
  • the improved method of the present invention broadly comprises in combination an adsorption step, a depressurization step, a purge step, a repressurization step, and a desorption step. More specifically, the method of the present invention comprises an adsorption step wherein at an elevated temperature and superatmospheric pressure a vapor phase mixture of straight chain and nonstraight chain including cyclic hydrocarbons is contacted with a molecular sieve selective adsorbent to adsorb the straight chain hydrocarbon components of the mixture therefrom in the pores of said adsorbent; the adsorption step is terminated; a depressuring step wherein the pressure of the adsorption step is reduced to a value below that employed in the adsorption step; the depressuring step is discontinued; a purge step wherein the laden adsorbent is contacted with a straight chain hydrocarbon in vapor phase to remove surface-adsorbed hydrocarbons and hydrocarbons in the void spaces of the bed therefrom at a prescribed
  • surface-adsorbed hydrocarbons as used hereinabove includes all adsorption on the sieve other than in the sieve cages (within the zeolite crystal).
  • the expression includes all the non-normal compounds adsorbed in the macropores of the sieve (inter-crystalline pores) as well as those adsorbed on the surface.
  • the method of the present invention is particularly adaptable for the production of high purity normal parafns in excellent yields in a rapid, etlieient and economical manner.
  • a further object is to provide an improved method of producing relatively high molecular weight straight chain hydrocarbons of a high degree of purity in commercially attractive yields from mixtures of such hydrocarbons and non-straight chain hydrocarbon.
  • a still further object is to provide an improved cyclic hydrocarbon separation process which is conducted in a relatively short period of time.
  • straight chain hydrocarbon any aliphatic or acyclic or open chain hydrocarbon which does not possess side chain branching.
  • Representative straight chain hydrocarbons are the normal parains and the normal oleins, monoor polyolens, including the straight chain acetylenic hydrocarbons.
  • the nonstraight chain hydrocarbons comprise the aromatic and naphthenic hydrocarbons as Well as the isoparai'linic, isoolenic hydrocarbons and the like.
  • Straight chain hydrocarbon-containing mixtures which are suitably treated for the separation of straight chain hydrocarbons therefrom include the various petroleum fractions such as a naphtha or a gasoline fraction, a diesel oil fraction, a kerosine fraction, a gas oil fraction and the like.
  • a typical hydrocarbon fraction which may be treated for the removal of straight chain hydrocarbons therefrom might have a boiling point or boiling range in the range 40-600 F. and higher and contain a substantial amount of straight chain hydrocarbons, e.g. 2-35% by volume and higher. More particularly, a hy drocarbon fraction to be treated and containing straight chain hydrocarbons might have an initial boiling point in the range 40-300 F. and an end point in the range of 15G-600 F. and higher.
  • a hydrocarbon fraction treated for the removal of straight chain hydrocarbons therefrom might have the following composition.
  • Hydrocarbon type Percent by volume Naphthenes 0-75 Aromatics 0-50 Acyclic saturates and unsaturates (including normal parafns, isoparaflins, normal oleiins and/or isooleiins) 2-90 Typical renery stocks or petroleum fractions which may be treated for the adsorptive separation of straight chain hydrocarbons therefrom are a wide boiling straight run naphtha, a heavy straight run naphtha, a light straight run naphtha, a catalytic cracked naphtha, a thermally cracked or thermally reformed naphtha, a catalytic reformed naphtha and the like, or a diesel oil or kerosene or gas oil fraction including mixtures thereof and wherein the hydrocarbon fraction or mixture may have been catalytically pretreated with hydrogen.
  • zeolites may be described as Water-containing aluminosilicates having a general formula wherein R may be an alkaline earth metal such.
  • a particularly suitable solid adsorbent for straight chain hydrocarbons is a calcium aluminosilicate, apparently actually a sodium calcium aluminosilicate, marketed by Linde Co., and designated Linde Molecular Sieve Type A or 5A-45.
  • the crystals of this particular calcium aluminosilicate have a pore size or opening of about 5A units, a pore size sufliciently large to admit straight chain hydrocarbons, such as the normal parallins and the normal olens, to the substantial exclusion of the non-straight chain hydrocarbons, i.e., naphthenic, aromatic, isoparaf- -nic and isoolefinic hydrocarbons.
  • This particular selective adsorbent is available in various sizes, such as in the form of Ms" or 1/16" diameter extrusions, or as a finely divided powder having a particle size in the range of 0.5-5.0 microns.
  • a selective adsorbent employed in the practice of this invention may be in any suitable form or shape, granular, spheroidal or microspheroidal.
  • the method of the present invention should be carried out in the vapor phase and under essentially isothermal conditions.
  • the particular operating conditions selected are dependent on the nature of the feed stream to the adsorption zone, the carbon number range of the feed stream and desired product stream as well as the carbon number distribution (relative amounts of each carbon number) within the range, the straight chain hydrocarbon content of the feed stream and the olefnic, sulfur, nitrogen and aromatic content thereof.
  • the feed stream preferably should be relatively low in olefins, sulfur, nitrogen and aromatic content and these impurities can be readily reduced to acceptable limits or removed in a manner well known in the art such as by mild hydrogenation involving mild catalytic reforming.
  • the feed stream should be relatively free from the lower molecular weight hydrocarbons such as in the range from about Cl-C as such light hydrocarbons complicate recovery of the desorbing medium.
  • vessels 14, 14A and 14B represent the same sieve case in three different phases of the operating cycle.
  • a vapor phase mixture of relatively high molecular weight straight chain and non-straight chain hydrocarbons is charged by way of lines and 12 into a lower end of an adsorption vessel 14 maintained at an elevated temperature and superatmospheric pressure containing a bed of synthetic calcium sodium aluminosilicatc of Type 5A structure such as a Linde 5A-45 Sieve therein.
  • the straight chain components of the feed mixture are adsorbed by the selective adsorbent.
  • the desorbent medium present in the adsorption etliuent is obtained from the previous cycle wherein during desorption, a portion of the desorbing medium is adsorbed by the sieve pores from which the higher molecular weight straight chain components have been removed.
  • the feed in line 10 to adsorption vessel 14 is discontinued.
  • the vessel 14A is depressured by venting through lines 26, 27, 28 and accumulator 54 maintained at about atmospheric pressure.
  • the purge step is begun.
  • a stream of desorbing medium contained in lines 40, 42 and 44 is introduced countercurrent to the ow of the feed stream 10 into vessel 14A at a prescribed space velocity/purge volume ratio and a purge effluent stream is Withdrawn therefrom by way of lines 26, 27 and 28 and passed to purge accumulator 54.
  • the repressuring step is commenced.
  • the flow of the stream of desorbing medium into vessel 14A by way of line 44 is continued to increase the pressure in the vessel to the selected desorbing pressure.
  • the selected desorbing pressure is attained in vessel 14A the desorption step is begun.
  • the desorbing medium in the vapor state is passed through lines 40, 42 and 43 into the adsorbent vessel 14B containing the straight chain hydrocarbon components adsorbed by the selective adsorbent.
  • the flow of the desorbing medium is also countercurrent to the feed tlow during the adsorption step.
  • Countercurrent desorption ow 2 (i.e., opposite to the flow in the vessel during adsorption) is highly desirable to assist in removing adsorbed straight chain hydrocarbons from the selective adsorbent.
  • the resulting desorption etiiuent is withdrawn from vessel 14B by Way of line 36 and passed through lines 38 and 39 to fractionator 60 wherein the desorbate and desorbing gas are separately recovered.
  • the adsorbed straight chain hydrocarbons in the desorbate are recovered from fractionator 60 by way of line 64.
  • the desorbing medium is recovered by way of line 62 and can be returned to line 40 for further use.
  • vessel 14B is depressured to attain the lower pressure used in the adsorption step land the cycle is repeated by introducing an additional quantity of fresh feed into vessel 14 by way of line 10 and line 12.
  • the adsorption step in the process of the present invention is carried out with the feed stream being in the vapor phase.
  • the particular adsorption temperature used varies with the type of charge stock, carbon number content thereof, and desired range of the straight chain hydrocarbons to be recovered from the charge stock.
  • a further requirement, which controls the upper temperature limit of the adsorption step is the need to avoid cracking of the charge stock. Keeping in mind these lower and upper temperature limitations, it has been found that a temperature range of about 575-675 F. in the adsorption step will permit excellent separations.
  • the adsorption vessel In the adsorption step, the adsorption vessel should be maintained at a positive pressure above atmospheric pressure to permit the selective adsorbent to absorb an additional quantity of normal straight chain hydrocarbons in the adsorption step. It has been found that maintaining the adsorption vessel at a pressure of between to 50 p.s.i.g. during the adsorption step affords good results in terms of rapid adsorption of the adsorbable components of the feed stream by the selective adsorbent.
  • the charge stock is introduced into the adsorption vessel at a selected rate and the feed is continued until the selective adsorbent is loaded with normal straight chain components of the feed.
  • Introduction of feed is preferably continued beyond the saturation point of the selective adsorbent for the normal straight chain hydrocarbon components of the feed and also beyond the point at which the straight chain components of the feed begin to breakthrough into the adsorption eluent (non-adsorbed portion of the feed).
  • Introduction of the feed into the adsorption vessel is preferably terminated when there is a normal parain overcharge of between about 0.5 and l5 weight percent.
  • Normal paraffin overcharge is defined as the amount of n-parafns in the feed stock to the adsorption vessel which is charged during the adsorption step in excess of the total amount on a weight basis of recovered normal parains during desorption and the normal parafns recovered in the depressuring and purge effluent Streams expressed as a percentage of normal parains charged.
  • the utilization of the selective adsorbent at maximum efficiency is a material factor in the process of the present invention because it compensates for the less than complete desorption of the adsorbed straight chain hydrocarbons in the subsequent desorption step.
  • the overcharge range of 0.5- ⁇ weight percent is suitable for excellent sieve utilization in a short processing time.
  • the adsorption vessel is depressured in a depressuring step to a lower pressure than the adsorption pressure.
  • This depressuring step is required to remove some of the surface adsorbed non-normal straight chain hydrocarbons from the selective adsorbent and to also begin to remove from the adsorption vessel, particularly from the void spaces between the selective adsorbent some of the unadsorbed portion of the charge stock while minimizing loss of the -adsorbed straight chain hydrocarbons from the sieve pores.
  • the depressuring step is terminated when the adsorption pressure is decreased to about atmospheric pressure, and advantageously in the range of 0-10 p.s.i.g.
  • the depressuring step is carried out at substantially the same temperature as was used in the adsorption step.
  • a purge step is begun using as the purge medium a vaporized stream of the material subsequently used as the desorbing medium.
  • the purge step is carried out at substantially the same temperature as the adsorption and depressuring steps, and at the reduced pressure attained in the depressuring step.
  • a stream of the vaporized desorption medium is introduced into the adsorption vessel in a direction countercurrent to the flow of the charge stock thereto.
  • the purge medium removes the remaining portion of the charge stock from the adsorption vessel and the surface adsorbed non-straight chain components from the selective adsorbent.
  • the purge step it is necessary to maintain the purge medium in the vapor state for eicient operation and the flow rate thereof at a value between 50 and 1000 vapor hourly space velocity and the purge gas volume at a value between 0.1 and 10 volumes and wherein the ratio of the purge medium rate to the purge volume is at least 40/1 and up to about 7000/1, preferably between 50 and 3500/1 to minimize removal of the pore adsorbed straight chain components of the feed stream and to maximize removal of surface adsorbed and the bed-entrapped contaminating components.
  • vapor hourly space velocity refers to the purge medium charge rate expressed as vapor volume (at purge conditions) per hour per volume of adsorbent.
  • purge volume refers to the amount of urge medium in the purge effluent stream per cycle and is equivalent to one vapor volume displacement (at purge conditions) of the total volume occupied by the sieve bed.
  • Most ecient operations are conducted using a purge medium velocity of to 680 ⁇ vapor hourly space velocity and a purge medium volume of 0.2 to 4.0 and a purge medium rate to purge volume ratio of at least 50/ 1 when it is desired to attain exceptionally high n-paraflin product purity.
  • the effluent from the purge step comprising purge medium, unadsorbed charge stock and surface adsorbed components of the charge stock together with some adsorbed n-parains removed from the sieve pores by the purge medium is returned to the fresh feed lines as a supplemental charge to the adsorption vessel. Routing of the purge effluent in this manner permits readsorption by the sieve of the normal straight chain hydrocarbon components of the feed that had been removed therefrom in the purge step. In addition the normal parains in the purge stream eiiluent are not lost to the process.
  • the vessel is repressured to the desorption pressure which is advantageously about 20-75 p.s.i.g., and preferably about 1-20 p.s.i.g. above the highest pressure in the sieve vessel ⁇ during the adsorption step.
  • This repressuring step is necessary to permit more rapid desorption of the pore adsorbed straight chain components from the adsorbent and to facilitate removal of these components from the sieve by the desorbing medium in the desorption step.
  • the desorption pressure is attained by discontinuing the olw of the purge eluent stream to the purge accumulator via line 28, while continuing the ow of purge medium into the adsorption vessel.
  • the rate of flow of the desorbing medium into the adsorption vessel is about 0.25-3 liquid hourly space Velocity (LHSV) to remove the pore adsorbed straight chain hydrocarbons from the sieve.
  • LHSV liquid hourly space Velocity
  • the desorbing medium employed is essentially of the same composition as the purge medium.
  • Use of the same hydrocarbon composition as the purge and desorption media avoids the problem of product contamination with other hydrocarbons while simplifying the processing requirements.
  • Choice of a suitable desorption medium for use in the practice of the present invention is largely dependent on the composition of the fresh feed, avails thereof and desired end product carbon number distribution. In general it has been found that most advantageous results are obtained when the desorption medium has a composition comprising a major amount of straight chain hydrocarbon or a mixture of straight chain hydrocarbons having an average of about 1 to 3 carbon atoms less than the lightest straight chain hydrocarbon in the fresh feed charge to the adsorption vessel.
  • Maintaining a carbon number spread of about 1 to 3 between the purge-desorption media and the fresh feed charge lightest component permits effective and rapid desorption times in the process of the present invention in addition to affording ease of separation of the desorbing medium from the desired product stream by fractionation.
  • a purge-desorption medium comprising about 80% by Weight of normal heptane has been found to be satisfactory.
  • a desorption medium composed of C10-C12 straight chain components has been found to give excellent results.
  • the present process provides a means of shortening the desorption time of prior processes by the combination of (a) using a desorbing medium in the vapor state and comprising in itself an adsorbable normal parain hydrocarbon and/or admixture of such normal paraffin hydrocarbons, (b) a desorption medium space velocity of 0.25 to 3 LHSV, and (3) additionally in terminating the desorption step when about l-35% by weight of the pore adsorbed straight chain hydrocarbon components remain in the sieve pores.
  • a desorbing combination will materially improve the desorption of the adsorbed straight chain components from the sieve pores. It has been found that at a desorption temperature of about 600 F.
  • n-heptane desorption medium in the desorption of nJCm-C components from the adsorbent pores at a desorption medium space velocity in the range of about 2.0 LHSV, volumes liquid desorbent/ hour/volume adsorbent, the adsorbed components can be removed to the extent of 80-90'% in from about -17 minutes; at a 0.5 LHSV in from about 23 to 42 minutes.
  • the flow of desorbing medium into the adsorption zone is countercurrent to the fresh feed charge which preferably is upow.
  • the lighter straight chain hydrocarbon components of the charge adsorbed in the pores of the adsorbent during the adsorption step are first desorbed, and, in turn, they assist the desorbing medium in desorbing of the adsorbed heavier straight chain hydrocarbon components nearer to the desorption outlet end of the vessel.
  • Termination of the desorption cycle short of essentialy complete removal of adsorbed straight chain hydrocarbons from the sieve pores permits the time of desorption to be materially decreased, i.e. in the order of 25-80%.
  • the throughput of the charge can be materially increased with the result that more charge stock can be treated per operating day and more product streams can be obtained.
  • the adsorption vessel is depressured to the adsorption pressure and the cyclic operation is repeated.
  • the process of the present invention is essentially a timed cycle process. It has been found that in cases where a relatively long desorption time is required satisfactory results have been achieved if the adsorption step is accomplished in about one-third of the total processing time, the remaining two-thirds being taken up by the balance of the processing steps, e.g. depressure., purge, repressure, desorption and depressure.
  • depressure., purge, repressure, desorption and depressure e.g. depressure., purge, repressure, desorption and depressure.
  • time sequence is advantageous i' adsorption7.5 minutes; depressure-QSO minute; purge-1.0 minute; repressure-OO minute; desorption-13 minutes; a total cycle time of 22.5 minutes.
  • adsorption step is about onehalf of the total processing time with the remaining onehalf being taken up with the depressure, purge, repressure, desorption and depressure steps.
  • the following time sequence is advantageous: adsorption-6.5 minutes; depressure-0-5 minute; purge- 0.5 minute; repressure--0-5 minute; desorption-5.0 minutes; a total cycle time of 13 minutes.
  • the time for the adsorption cycle is about one-third of the total cycle time and with a two vessel per set system the adsorption cycle time is equal to one-half of the total cycle time.
  • valves in lines 26, 36, 41, 43 and 44 are in the closed position.
  • the valve in line 41 opens and permits the desorbing medium maintained in the lines 40 and 41 under pressure and at elevated temperature, to be bypassed around the adsorption vessel.
  • the valve in line 26 is opened to decrease the pressure in the adsorption vessel 14A (on the purge cycle) ⁇
  • the valve in line 44 is opened to permit passage of a stream of desorbing medium into vessel 14A for the purging step.
  • the vessel is repressured by the ow of the stream of desorbing medium into the vessel until the desorption pressure is reached.
  • valves in lines 41 and 44 are then closed and the valves in lines 43 and 36 are opened substantially simultaneously with the closing of valves in lines 41 and 44.
  • valves in lines 43 and 36 are closed. lOperating with this valve switching sequence permits the yield of high purity normal parains to be increased without damaging the sieve bed by pressure variations during this portion of the cycle.
  • This embodiment further permits use of low purge volume displacements during the purge step and minimizes the loss of adsorbed normal parans from the sieve pores during the purge cycle.
  • adsorption effluent stream comprising 76.8 weight percent C10-C15 nonstraight chain hydrocarbons and 1.6 weight percent C10- C15 straight chain hydrocarbons and 21.6 weight percent desorbing medium at a rate of 6140 cc./hr.
  • the recovered adsorption effluent was fractionated and there was separately recovered C10-C15 non-straight hydrocarbons in a yield of 84.4 weight percent basis fresh feed.
  • the selective adsorbent adsorbed the straight chain hydrocarbon components of the feed to the extent that after about 8.5 minutes on the adsorption cycle, the adsorbent Was substantially saturated with the straight chain components.
  • the ow of feed was continued to the adsorption zone until a total time ⁇ of 13.0 minutes had elapsed at which time there was a 10% overcharge of straight chain hydrocarbons therein.
  • the feed into the adsorption vessel was then discontinued and the vessel depressured to about atmospheric pressure in 0.5 minute.
  • a purge stream of the desorbing medium in the vapor state and comprising 84.3 weight percent n-heptane, the balance being branched chain and cyclic parains in the 204- 237 F. boiling range was passed into the adsorption vessel at a rate of 170 vapor hourly space velocity (at purge conditions) and countercurrent to the direction of charge stock fed thereto.
  • the -ow of purge medium was continued until 2.6 purge volumes had been fused and the ratio of the purge rate to the purge volume was 65/1.
  • the purge eiuent comprising 19.9 weight percent vessel was depressured and switched to the adsorption step and the processing sequence was repeated.
  • the yield of C10-C15 straight chain hydrocarbons was 90.0 weight percent, basis straight chain hydrocarbons in the fresh feed.
  • the C10-C15 straight chain hydrocarbon product contained 99.6 Weight percent normal straight chain hydrocarbons by weight.
  • Example II The procedure of Example I was repeated in this example except that the adsorption cycle time was 13 minutes, the purge time was 1.1 minutes and 3.2 volumes of purge medium were used. The results are summarized in Table A below.
  • Example I COMPARATIVE EXAMPLE A The procedure of Example I was repeated in this example except that the adsorption cycle time was 15.3 minutes, the purge time was 5.7 minutes, the purge volume was 3.2 and the purge vapor hourly space velocity of the 34 Vo/hL/Va. The results are summarized in Table A below.
  • the desorbing medium having the same composition as the purge medium described hereinabove was passed into the adsorption vessel in the same direction as the purge medium (countercurrent to the feed on the adsorption cycle) at a rate of 0.6 LHSV (Vo/hL/Va) to repressure the vessel to the desorption pressure of about p.s.i.g.
  • the repressuring operation was completed in about 0.3 minute.
  • desorbing medium was continued for the remainder of the 24.6 minutes desorption cycle and there was recovered a desorption ellluent which on subsequent separation yielded the following fractions: C10-C15 straight chain hydrocarbons, 15.6 weight percent yield, basis fresh feed, 77.8 weight percent desorbing medium, basis total desorbing medium feed (including purge).
  • the separated desorbing medium was reused in the next sequence.
  • the flow of desorption medium to the adsorption vessel was discontinued when about 80% of the pore adsorbed straight chain components had been removed from the sieve pores.
  • the desorption time was 24.3 minutes.
  • adsorption step a feed mixture of C10-C20 straight chain and non-straight chain hydrocarbons is introduced into an adsorption zone at an elevated temperature and superatmospheric pressure to eiect adsorption of the straight chain hydrocarbon components by the molecular sieve selective adsorbent of Type 5A structure in said adsorption zone, from said Zone as adsorption effluent is withdrawn comprising the non-straight chain hydrocarbon components of said mixture, the adsorption step is terminated when the adsorption zone has been normal paraflin overcharged in an amount between 0.5 and 15% by weight, a depressure step wherein the adsorption zone is depressured to a pressure less than the pressure in the adsorption step and then terminated, a.
  • a purge gas medium of a desorbing medium comprising a major amount of at least one straight chain hydrocarbon having an average of about l to 3 carbons less than the lightest straight chain hydrocarbon in the feed mixture introduced into the adsorption zone is passed into the depressured adsorption zone to remove surface adsorbed components of the feed mixture therefrom, the purge step is terminated, a repressure step wherein the adsorption zone is repressured to a pressure greater than the said adsorption pressure and then terminated, a desorption step wherein a desorbing medium having the same composition as the purge gas medium is introduced into the repressured adsorption zone to effect removal of the adsorbed straight chain hydrocarbon components from the selective adsorbent, a desorption effluent is withdrawn, and the straight chain hydrocarbon cornponents of the feed mixture are recovered therefrom, the desorption step is terminated, a second depressuring step wherein the pressure in the adsorption zone is decreased to the pressure of
  • a process for the separation of C10-C20 straight chain hydrocarbons from a petroleum fraction which comprises in an adsorption step contacting said petroleum fraction in the vapor phase at an elevated temperature and pressure and with a 5A type molecular sieve selective adsorbent to adsorb the straight chain hydrocarbons, in a purge step at a lower pressure countercurrently contacting said molecular sieve with a purge medium comprising a major portion of straight chain hydrocarbons having a lower molecular weight by 1-3 carbon atoms than the lightest straight chain component of the petroleum fraction, at a purge medium rate of between 50 to 1000 -vapor hourly space velocity and a purge medium volume in the range of 0.1 to 10 volumes of vapor per unit bed Volume and wherein the ratio of the purge medium rate to the purge medium volume is between 40/1 and 7000/1, and in a desorption step at a higher pressure than the adsorption pressure, removing the adsorbed straight chain hydrocarbons from the molecular sieve with a gase

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3619418A (en) * 1969-06-30 1971-11-09 Texaco Inc Storing desorbent separated from adsorption effluent
EP0043610A1 (en) * 1980-07-07 1982-01-13 Shell Internationale Researchmaatschappij B.V. Process for the resolution of a hydrocarbon mixture
US4619758A (en) * 1982-07-09 1986-10-28 Texaco, Inc. Fluid catalytic cracking method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4350501A (en) * 1981-03-27 1982-09-21 Shell Oil Company Absorption process

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3183182A (en) * 1961-09-08 1965-05-11 British Petroleum Co Prolongation of sieve capacity by controlled desulfurization
US3373103A (en) * 1966-02-01 1968-03-12 Texaco Inc N-hydrocarbon separation with a molecular sieve

Family Cites Families (2)

* Cited by examiner, † Cited by third party
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CA713894A (en) * 1959-11-25 1965-07-20 The British Petroleum Company Limited Separation of mixtures
FR1381943A (fr) * 1963-02-10 1964-12-14 British Petroleum Co Procédé de séparation d'hydrocarbures à chaîne droite de leurs mélanges avec des hydrocarbures à chaîne ramifiée et cycliques

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3183182A (en) * 1961-09-08 1965-05-11 British Petroleum Co Prolongation of sieve capacity by controlled desulfurization
US3373103A (en) * 1966-02-01 1968-03-12 Texaco Inc N-hydrocarbon separation with a molecular sieve

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3619418A (en) * 1969-06-30 1971-11-09 Texaco Inc Storing desorbent separated from adsorption effluent
EP0043610A1 (en) * 1980-07-07 1982-01-13 Shell Internationale Researchmaatschappij B.V. Process for the resolution of a hydrocarbon mixture
US4619758A (en) * 1982-07-09 1986-10-28 Texaco, Inc. Fluid catalytic cracking method

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FR2003637B1 (nl) 1974-03-15
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DE1911859A1 (de) 1969-10-16
NL151734B (nl) 1976-12-15
BR6906956D0 (pt) 1973-01-02
ES364495A1 (es) 1971-02-01
SE362065B (nl) 1973-11-26
FR2003637A1 (fr) 1969-11-14

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